Dis-benzothiazolylazo dyes



3,485,813 DlS-BENZUTHIAZGLYLAZG DYES Max A. Weaver and John 1. Dale,Kingsport, Tenn, as-

signors to Eastman Kodak Company, Rochester, N.Y., a corporation of NewJersey No Drawing. Filed July 11, 1966, Ser. No. 564,011 lint. Cl. ll9b33/06 U5. Ci. 260-158 8 Clm'ms AESTRAiIT F THE DESCLGSURE Disazocompounds containing two benzothiazolyl-azoaniline moieties joined bythe group -CH CH SO CH CH which is attached to the nitrogen atom of eachaniline coupling component. The disclosed compounds are useful fordyeing hydrophobic textile materials.

This invention relates to novel disazo compounds and, particularly, toWater insoluble disazo dyes for hydrophobic textile materials.

The novel disazo compounds of the invention are characterized by thegeneral formula (I) R R RN=NR1N N-R -N=NR CHQCHQSOZCHZCHQ wherein R is abenzothiazolyl group having the structure wherein Y, in R and R can bethe same or different and represents hydrogen, alkyl, e.g. methyl,ethyl; alkoxyl, e.g. methoxyl, e.g. acetamido; halogeno, e.g. chloro,bromo; benzamido; benzylamino; N-alkylarylamino, e.g. Nmethylphenylamino, dicarboxylicacidimido, e.g. succinimido; alkylthio,e.g. methylthio; aryloxyl, e.g. phenoxyl; combinations thereof; and nrepresents 1, 2 or 3; and

R and R can be the same or different and represent hydrogen or an alkylradical, preferably lower alkyl, i.e. from 1 to 4 carbon atoms, beingunsubstituted or substituted such as hydroxyalkyl, e.g. hydroxyethyl,polyhydroxyalkyl, e.g. 2,3-dihydroxypropyl, alkoxyalkyl, e.g.rnethoxyethyl, cyanoalkyl, e.g. cyanoethyl, cyanoalkoxyalkyl, e.g.beta-cyanoethoxyethyl, e.g. acetoxyethyl, haloited States Patent 0 icegenoalkyl, e.g. chloroethyl, alpha-chloropropyl, bromoethyl,hydroxyhalogenoalkyl, e.g. beta chlorogamma hydroxy, alkylsulfonylalkyl,e.g. methylsulfonylethyl, alkyl- OCOOCH CH e.g., CH OCOOCH CH alkyl,e.g. dicarboxylic acid imidoalkyl, e.g. succinimidoethyl; benzyl;phenoxyalkyl, e.g. beta-phenoxyethyl; alkylsulfonamidoalkyl, e.g.methylsulfonamidoethyl; carbamatoalkyl, e.g. carbamatoethyl; and thelike. Preferably, the alkyl moiety of the substituents represented by X,Y, R and R have up to about four carbon atoms.

The disazo compounds of the invention are prepared by coupling theconventional diazonium salts of compounds having the formula (II) RNHwith unsymmetrical coupling components having the (formula wherein R andR may be the same or different and R and R may be the same or differentbut either R must be different than R or R must be different than R orWith symmetrical coupling components having the formula Ar N H ArN NAr(3211450202112 wherein Ar and Ar represents either R or R of Formula Iwherein R and R are the same or different and R and R are the same ordilferent but either R is different than R or R is different than R andare defined as set forth in Formula I.

The symmetrical couplers of Formula IV are prepared by reacting twomoles of an appropriately substituted aryl amine with one mole ofdivinyl-sulfone in the pres ence of acetic acid catalyst, as set forthin the following illustrative sequence:

R (01 R N\ S O 2 E 02113 3 R (or R wherein Ar=R =R and R :R and whereinR R R and R are defined above in Formula I.

The following examples will serve to illustrate the preparation ofrepresentative couplers and disazo compounds of the invention. As willbe seen from the examples, the substituents X, Y, R and R as defined inFor- HOAe 3 4 mula I serve primarily as auxochrome groups to control wasstirred 1.75 hr. at C., then added to a solution or the color of thedisazo compound. 3.88 g. bis[Z-(N-ethyl-m-toluidino)ethyl] sulfone in100 ml. 15% sulfuric acid, all at about 5 C. The coupling PREPARTIONSYMMETRICAIT ,COUPLERS was continued at this temperature for 2 hr., thenPreparatlon of bls [2(N'eth3'1'm't1u1dm)ethyl] drowned with water,filtered, washed with water, and

Sulfone 5 air dried. The product dyes cellulose acetate and poly- Anamount of 27.0 g. N-ethyl-m-toluidine, 11.8 g. diester fibers abrilliant red shade with good fastness propvinylsulfone, 5 cc. glacialacetic acid, and 50 cc. toluene erties. This dye had the structure:

N I 2 5 C2115 CH SO N-N N N N'N O CH 3 2\/ S s b 2 CQHqSOzCgH; C113 CH3was refluxed for 24 hr. The toluene and acetic acid were EXAMPLE 2removed under vacuum and the residue taken up in 150 ml. of ethanol.This solution was chilled for 2 hr. at m1 conc H2504; the solution was60016 d in an ice bath near 0 C. and the white crystalline product wascol- 20 to about 0 C- and 20 mL 15 acid (1 part propiomc looted byfiltration. Yield 2.14 g. M.P. 5861. It had the acidfi parts aceticacid) was added below G Then Structure: at below 10 C., 3.50 g.2-amino-6-cyanobenzothiazole was added followed by ml. 1:5 acid. Thereaction Sodium nitrite (1.44 g.) was added portionwise to 10 CZHE H50;was stirred 2 hr. at 05 C. and added to a solution of Q 4.05 g. ofbis[2-(N-beta-hydroXyethyl-m-toluidino)2- ethyl]sulfone in 100 ml. 1:5acid at 5 C. Solid am- CH3 monium acetate was added until the solutionturned Congo Red paper brown and the coupling allowed to stand 2 hr. atice bath temperature. It was then drowned with water, filtered, washedwith water and air dried. It dyes cellulose acetate a bright red shade,and had the The above procedure was repeated, substitutingN-betafollowing structure:

Preparation of bis[2-(n-beta-hydroxyethyl-m-toluidino) ethyl] sulfoneOzH iOH HOH4C2 CH3 CH3 hydroXyethyl-m-toluidine for N-ethyl-m-toluidine.The EXAMPLE 3 product had the structure:Z-amino-6-methylsulfonylbenzothiazole (4.56 g.) was 0213403: 11011 0diazotized as in Example 1 and added to a solution of 3.60 g.bis[2-(N-ethylanilino)ethyl]sulfone in 100 ml. 15 H all at 0-5 C. Thecoupling was continued I 0213480202114 I I at this temperature for 2hr., then drowned with water.

CH3 filtered, washed with water, and the product air dried. Inaccordance Wlth the above prcccdurcs, -(N- It dyed polyester fibers redand had the structure W 2115 12115 i CHBSOF o-N=N -N otnisoioinm 8 01cms s EXAMPLE 4 2-amino-6-methylsulfonylbenzothiazole (4.56 g.) wasdiazotized and coupled with 3.60 g. bis[2-(N-methyl-mtoluidino)-ethyl]sulfone as illustrated in the above examples. This dyecolored polyester fibers red. It had the structure:

ethylanilino)ethyl]sulfone was prepared from N-ethylaniline anddivinylsulfone and 'bis[2-(N-methyl-m-toluidino)ethyl]-sulfone wasprepared from N-rnethyl-mtoluidine and divinyl-sulfone.

PREPARATION OF SYMMETRICAL DYES EXAMPLE 1 The disazo compoundsillustrated in the following table A solution f 4,56 of2,-amino-6-methylsulfonylare prepared by the procedure illustrated inExamples 1 benzothiazol in 100 g. 50% aqueous sulfuric a id was to 4,above. Thus, the appropriate compounds of Formula cooled to 5% C. and asolution of 1.44 g. of NaNO II are coupled with suitable couplers ofFormula IV to dissolved in 10 m1. conc. H 80 was added, keeping theobtain the compounds of Formula I wherein R R and temperature less than0 C. The diazotization reaction R =R TABLE Example Substituent (X) on RR R Phenylene m-Tolyle 2,5-di-CH3-pheuy1ena m-NHCOCHS phenylene 31-B-SOnNHCHa- 32 4,6-dichlor 33.. G-bromo g4 6-NHCOCHa- PREPARATION OFUNSYMMETRICAL COUPLERS Preparation of 2- [N- Z-N-ethyl-m-toluidino)-ethyl] -2'- [N- (N-ethyl-m-chloroanilino) ethyl] sulfone An amount of25.3 g. N-ethyl-N-beta-vinylsulfonylethyl-m-toluidine, 15.5 g.N-ethyl-m-chloroaniline, 5 ml. acetic acid and 50 ml. toluene wasrefluxed for 24 hr. The toluene and acetic acid were removed undervacuum and the residue crystallized from ethanol. The coupler had thestructure:

Hr Q (IJH C2H4SO2Cz 4 (1:1

PREPARATION OF UNSYMMETRICAL DYES EXADIPLE 38 A diazonium solution wasprepared from 4.56 g. of 2-amino-6-methylsulfonylbenzothiazole asdescribed in Example 1, and added to a solution of 4.08 g. of Z-[N-(Z-ethyl-m-toluidino) ethyl] 2' [N ethyl-m-chloroanilino)ethyl]sulfonein ml. 15% sulfuric acid all at 5 C. The coupling was continued 2 hr.then it was drowned with water, filtered, washed With water and airdried. The dye dyed cellulose acetate and polyester fiber red shades ofgood fastness. The dye had the structure:

C2 5 CzHs N N I! l CHM M N Ml S S I CzHlS 0 2C 2H4 Preparation of2-[N-(ethyl-2,5-dimethoxy-anilino) ethy 2-[N-(N-beta-vinylsulfonylethyl] aniline) An amount of 29.9 g.2,5-dimethoxy-N-ethyl-N-betavinylsulfonylethylaniline 13.7 g.N-beta-hydroxyethylaniline 5 ml. acetic acid and 50 ml. toluene wasrefluxed for 24 hr. The toluene and acetic acid were removed underreduced pressure and the viscous oil obtained was used without furtherpurification. The coupler had the structure:

CHgO

EXAMPLE 39 0 C Ha N C2115 HOC2H4 7 8 The disazo compounds in thefollowing table are preaqueous dispersions in the manner of theso-called dispared by the procedure illustrated in Examples 38 andpersed dyes. However, coloration can also be effected. 39, above. Thus,the appropriate compounds of Formula for example, by incorporating thecompounds into the II are coupled with suitable couplers of Formula IIIto spinning dope and spinning the fiber as usual.

The compounds of the invention are not necessarily obtain the compoundsof Formula I wherein R R all equivalent as dyes. The degree of dyeaffinity varies,

and R and R may be the same or different. 5

TABLE Example Substituent (X) on R R R R R 40 6-CH3SO2 Phonylenem-Tolylene 6-NO2 m-CHao-phenylene .d

6-SO CH2OH OH" m-NHCOCH; pheny1ene- C2H4OCH3 S-CH; 2CH3O-5-CH3 phenyleneC H CO CQH= The disazo compounds of the invention can be used forexample, depending upon the material being dyed for dyeing textilematerials, including protein and synand the formula of the disazocompound. Thus, for exthetic polymer fibers, yarns and fabrics, giving avariety ample, all the compounds will not have the same degree of fastbrilliant violet to red shades when applied thereto of dye affinity forthe same material. Accordingly, the by conventional dye methods. Thedisazo compounds substituents X and Y and the substituents R and R ashave high affinity for cellulose ester, polyester, and nylon mentionedabove, serve primarily as auxochrome groups fibers. When the compoundsare used for dyeing such to control the color of the disazo compound.hydrophobic materials, they should be free of water- Polymeric linearpolyester materials of the terephthalsolubilizing groups such as sulfoand carboxyl. In general, ate type are illustrative of the lineararomatic polyester the dyes have excellent fastness, for example, tolight, textile materials that can be dyed with the new disazo washing,gas (atmospheric fumes) and sublimation. The compounds of the invention.The terephthalate fibers sold dyes are outstandingly sublimationresistant on polyesters. under the trademarks Kodel, Dacron, andTerylene,

As described above, the present disazo compounds for example, areillustrative of the polyester textile matehave the characteristicstructure of Formula I. This disrials that can be dyed. Kodel polyesterfibers are more tinctive structure imparts unexpected properties to theparticularly described in U.S. Patent 2,901,446. Dacron compounds,including the above'described light fastness and Terylene polyesterfibers are described, for example, and sublimation resistance. Thus, thecompounds of the 40 in U.S. Patent 2,465,319. The polymeric linearpolyester invention have been found to possess excellent propermaterialsdisclosed in U.S. Patents 2,945,010,; 2,957,745 ties when tested bymethods such as described in the and 2,989,363, for example, can bedyed. The linear A.A.T.C. Technical Manual, 1964 edition. aromaticpolyester materials specifically named have a The compounds of theinvention can be used for dyemelting point of at least 200 C. inghydrophobic fibers such as linear polyester, cellulose Nylon in fiber,yarn and fabric form, is representative ester, acrylic, polyamide, etc.,fibers in the manner deof polyamides which can be dyed with the disazoscribed in U.S. Patents 2,880,050; 2,757,064; 2,782,187 compounds. and2,043,827. The following example illustrates a The invention has beendescribed in considerable detail method by which the disazo compounds ofthe invention with particular reference to certain preferred embodicanbe used to dye polyester textile materials. ments thereof, but will beunderstood that variations and 0.1 g. of the dye is dissolved in the dyepot by warmmodifications can be effected within the spirit and scope ingin 5 cc. of ethylene glycol monomethyl ether. A 2% of the invention.sodium-N-methyl-N-oleyl taurate and 0.5% sodium lig- We claim: ninsulfonate aqueous solution is added, with stirring, 1. Adisazo compoundhaving the formula until a fine emulsion is obtained. Water is thenslowly X is hydrogen, lower alkyl, lower alkoxyl, lower added to a totalvolume of 200 cc. Then, 3 cc. of Dacalkanoyl, formyl, trifiuoromethyl,acetamido, nitro, ronyx (a chlorinated benzene emulsion) are added andchlorine, bromine, lower alkylsulfonyl, lower cyano- 10 grams of atextile fabric made of Kodel polyester alkylsulfonyl, lowerhydroxyalkylsulfonyl, cyano, carfibers are entered. The fabric is worked10 minutes withbamoyl, N-lower alkylcarbamoyl, benzamido, lower out heatand then for 10 minutes at 80 C. The dye bath alkoxycarbonyl,loweralkylsulfonyl, sulfarnoyl, N- is then brought to the boil and heldat the boil for one lower alkylsulfamoyl, succinimido, thiocyanato,lowhour. Following this, the fabric is rinsed in warm water, eralkylthio, phenoxyl or benzoyl; then scoured in aqueous 0.2% soap, 0.2%soda ash mislor 2; solution. After scouring, the fabric is rinsed withwater Y is hydrogen, lower alkyl, lower alkoxy, chlorine broand dried.Accordingly, since the compounds of the inmine, acetamido, or benzamido,each Y being the vention are water-insoluble, they can be applied fromsame or different;

3,485,813 9 10 n is 1 0r 2;

R and R are the same or different and each is hydrogen, lower alkyl, orlower alkyl substituted with hydroxy, lower alkoxy, chlorine, bromine,cyano, acetoxy, lower carbalkoxy, lower alkylsulfonyl, lower a1kyl-OCOO,CONH succinirnido, phenyl, 5 phenoxy, or lower alkylsulfonamido.

2. A disazo compound according to claim 1 having the formula N N i IL BK=i N- N=N C2H4SO2C2H4 Y(n) wherein 4. A disazo compound according toclaim 1 having the formula 5. A disazo compound according to claim 1having the formula SOzCH;

6. A disazo compound according to claim 1 having the formula C H; CH2

7. A clisazo compound according to claim 1 having the formula C'zHsC2115 1 1 1 2 8. A disazo compound according to claim 1 having theformula -N OCH: N-

| CzHs HOCzHA I ll I NG- /N=N N N- N: CN s s CzH4SO2C2H4 OCH;

CHARLES B. PARKER, Primary Examiner DONALD M. PAPUGA, Assistant ExaminerReferences Cited UNITED STATES PATENTS 2,128,256 8/1938 Krzikallaetal260 199 15 3,271,383 9/1966 Yamayaetal 26o 1ss s-4, 41, 55; 260-40,570.5

